US4746568A - Heat-resistant coating composition and heat-resistant coat - Google Patents
Heat-resistant coating composition and heat-resistant coat Download PDFInfo
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- US4746568A US4746568A US07/013,815 US1381587A US4746568A US 4746568 A US4746568 A US 4746568A US 1381587 A US1381587 A US 1381587A US 4746568 A US4746568 A US 4746568A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a heat-resistant coating composition and a heat-resistant coat making use of said composition, and more particularly to a heat-resistant coating composition and a coat consisting of said composition which has stable rust-proofness even after it has been exposed to any temperature within a temperature range of -50° C.-650° C. for a long period.
- An exhaust pipe of a motor car engine is composed of an exhaust pipe section connected to an exhaust manifold or directly to cylinder heads and a muffler (silencer); the closer a portion of the exhaust pipe is located to the engine, the larger temperature change to which said portion is exposed, and at the rear end portion of the muffler which is remote from the engine, the temperature change is 100° C. or lower.
- the condition of use of the exhaust pipe section close to the engine is especially severe, in a cold district it is used in the temperature range of, for instance, from an atmospheric temperature -30° C. to about 650° C. upon high speed rotation of the engine, and moreover, upon starting of the engine the temperature rises at a rate of about 600° C. per minute and reaches the highest temperature after only about 70 seconds.
- a silicone series heat-resisting paint As a heat-resisting coating material for protecting an exhaust pipe, a silicone series heat-resisting paint has been used, and the composition of the paint consists principally of silicone resin or modified silicone resin, metallic zinc and inorganic pigment.
- a metal surface to which this composition is to be applied is preliminarily roughened by subjecting it to a shot blast treatment, the above-mentioned composition is applied on the roughened surface to form a lower layer, then a composition consisting of silicone resin, metal oxides and inorganic pigment is superposed thereon, and thereby a heat-resisting coat is formed.
- the principle of rust-prevention by means of this heat-resisting coat is such that in the low temperature range, invasion of water and salts which act as corrosive media to the surface of metal is prevented by the coat, and after heating, it is aimed to realize a sacrificial anodic effect of metallic zinc making use of a potential difference between the base metal and zinc.
- the heat-resisting coat in the prior art there exists a temperature range where either of the above-mentioned rust-preventing effects appears poorly, and more particularly, a rust-prevention power after heated in the temperative range of 200° C.-300° C. is poor, and so, on the practically used exhaust pipe, often rust was produced at an early time.
- the thickness of the coat is 60 ⁇ or less, and so, in the case where the height of the protrusions formed on the metal surface by the roughening treatment exceeds 40 ⁇ , the thickness of the coating layer covering the protruded portions is remarkably reduced, hence the top portions of the protrusions are apt to be exposed, and thus rusting is promoted.
- a principal object of the present invention is to provide a heat-resisting coating composition which does not produce assembled cracks even when it is heated, in which a sacrificial anodic effect relying upon metallic zinc can be fully achieved, and which has an excellent rust-preventing property.
- Another object of the present invention is to provide a heat-resisting coat which is applied on a surface of metal subjected to a special surface roughening treatment, which is hard to be peeled off and which has an excellent rust-preventing property.
- FIG. 1 is a photograph showing the state where cracks have been produced by heating a publicly known heat-resisting coat containing particles of inorganic material powder;
- FIG. 2 is a photograph showing the state where particles of a pulverized inorganic material are exposed by heating a heat-resisting coat according to the present invention
- FIG. 3 is a cross-section view of a metal surface portion attained through a surface roughening treatment in the prior art
- FIG. 4 is a cross-section view showing the state where a heat-resisting coat has been applied onto the metal surface shown in FIG. 3;
- FIG. 5 is a cross-section view showing the state where a heat-resisting coat has been applied onto a metal surface attained through a surface roughening treatment relevant to the present invention.
- FIGS. 6 to 9 are comparative diagrams showing the effects of heat-resisting coats according to the present invention.
- the heat-resisting coating composition according to the present invention comprises pulverized inorganic material consisting essentially of a mixture of powder containing at least one compound selected from the group consisting of aluminium phosphate, zinc molybdate and calcium carbonate, plate shaped powder particles consisting mostly of aluminium silicate or magnesium silicate, and metallic zinc powder, which inorganic material is bound by modified silicone resin to which an aluminium chelate compound has been added.
- pulverized inorganic material consisting essentially of a mixture of powder containing at least one compound selected from the group consisting of aluminium phosphate, zinc molybdate and calcium carbonate, plate shaped powder particles consisting mostly of aluminium silicate or magnesium silicate, and metallic zinc powder, which inorganic material is bound by modified silicone resin to which an aluminium chelate compound has been added.
- pulverized inorganic material consisting essentially of a mixture of powder containing at least one compound selected from the group consisting of aluminium phosphate, zinc molybdate and calcium carbonate,
- the strain caused by heating is dispersed among the particles of the powder, resulting in exposure of the surface of metallic zinc in the pulverized inorganic material, hence a sacrificial anodic effect can be revealed, and also invasion of water and salts which act as corrosive media can be surely prevented.
- a preferable compounding ratio of the heat-resistant coating composition according to the present invention is as follows:
- modified resin any one of phenol resin, epoxy resin, acrylic resin and polyester resin or a mixture of them (called modified resin) be present in the silicone resin to the extent 20-40 weight % (this being called modified silicone resin) and to add an aluminium chelate compound thereto.
- modified silicone resin ethylacetate aluminium di-isoprolylate or aluminium tris-ethylacetoacetate is favourable.
- the aluminium chelate compound functions as a catalyst for inter-molecule bonding in the resin, and it has the effect that by reducing the presence of unbonded molecules thermal decomposition loss is decreased and strength is improved, resulting in reduction of the network of cracks over the surface of the pulverized inorganic material (See FIG. 2). Also, the addition of modified resin to silicone resin is for the purpose of reinforcing adhesion when the composition is heated up to 350° C.-450° C. and giving it basic strength to reduce particle surface cracks.
- any one of aluminium phosphate, zinc molybdate and calcium carbonate or a mixture of them be present in the pulverized inorganic material to the extent of 20-55 weight %, and also it is desirable that the plate-shaped powder particles be present in the pulverized inorganic material to the extent of 2-30 weight %.
- mica powder principally consisting of aluminium silicate or talc principally consisting of magnesium silicate are effective, and these powders form a layer overlapping with other powder particles in the bonded coating composition. This layer has an excellent shielding effect and a capability of preventing a network of cracks.
- the metallic zinc powder to be used as a sacrificial anode it is necessary that it be present to the extent of 40-70 weight % in the above-described pulverized inorganic material and preferrably 20-56 weight % in the coating composition.
- the condition of the metal surface on which the above-mentioned heat-resisting coating composition is to be applied is also important.
- a shot-blast process and a sand blast process have been employed, and on the surface of metal treated through these processes are formed protrusions 1 having a cross-section configuration as shown in FIG. 3.
- fine protrusions 3 having "turn-rounds" (overhanging portions) 4 are formed on the surface of metal so as to improve adhesion of the coat 5 (FIG. 5). Since the protrusion 3 is formed as bent into the recessed portion by collapsing a tip portion of a simple spike-shaped protrusion and thus has a small height and a "turn-round” 4, an excellent heat-resisting power and an excellent high-temperature adhesion can be provided. In contrast to the fact that in the case of the metal surface configuration as shown in FIG. 3, even if the base metal is stainless steel or nickel plating having little tendency for thermal oxidation, a coat would peel off when heated up to 550° C. or higher, a coat applied to base metal having a group of fine protrusions with "turn-rounds" 4 formed thereon would not peel off even if it is heated up to 650° C. for a long period of time.
- protrusions 3 For forming such protrusions 3 on the surface of metal, it is sufficient to form fine protrusions and recesses on the metal surface by blasting metal particles, alumina particles, sand particles or the like having sharp corners and a diameter of 0.3 mm or less (particles which are called "grit") onto the metal surface with a high pressure by means of a blasting machine (for example, that of rotary blade type or compressed air type), and then collapsing the tip ends of the already formed fine protrusions by blasting spherical particles or rectangular particles of glass, metal or the like having a diameter of 0.3 mm or less with an extremely low pressure (See Example VIII).
- a blasting machine for example, that of rotary blade type or compressed air type
- the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated.
- the compounding proportions are shown in Table-3, and the test results are shown in Table-4.
- the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of pulverized inorganic material contained in the coat is 50-80 weight %, or when the proportion of "modified silicone resin+aluminium chelate compound" contained in the coat is 20-50 weight %.
- the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated.
- the compounding proportions are shown in Table-9, and the test results are shown in Table 10.
- the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of plate-shaped powder particles (mica+talc) contained in the pulverized inorganic material (zinc molybdate+metallic zinc powder+plate-shaped powder) particles is 2-30 weight %.
- Samples A, B, C and D have the resin component in the coat varied, Samples A and C employ modified silicone resin, and especially in Sample A the resin component is added with aluminium chelate compound.
- Samples A-1, B-1, C-1, and D-1 in place of silica which is an inorganic material component in Samples A, B, C and D, respectively, "silica+zinc powder" is used.
- Samples A-2, B-2, C-2 and D-2 the silica contents in Samples A-1, B-1, C-1 and D-1 are reduced, and condensed aluminium phosphate, zinc molybdate and calcium carbonate are added in place of them.
- Samples A-3, B-3, C-3 and D-3 the silica contents in Samples A-2, B-2, C-2 and D-2 are reduced, and mica and talc are added in place of them.
- heat-resisting coating film in the prior art means a coating film including, as a lower layer, a composition consisting of 30 wt.% silicone resin, 8 wt.% condensed aluminium phosphate, 8 wt.% zinc molybdate, 8 wt.% calcium carbonate, 35 wt.% zinc powder and 11 wt.% silica and another composition superposed thereon consisting of 26.3 wt.% silicone resin, 28.1 wt.% metal oxides, 19.3 wt.% silica and 26.3 wt.% talc, and that the above-referred "coat according to the present invention” means a coating film including, as a lower layer, a composition consisting of 20.4
- the heat-resisting coat according to the present invention a network of cracks would not be produced by heating, the surface of the metallic zinc particles in the pulverized inorganic material can be easily exposed, resulting in a sacrificial anodic effect, and invasion of corrosive media can be surely prevented. Moreover, the same heat-resisting coat applied onto a base metal surface provided with a group of fine protrusions having "turn-rounds" would hardly peel off even at a high temperature and thus reveals excellent corrosion proofness.
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Abstract
A heat-resisting coating composition prepared by binding with a mixture of modified silicone resin and an aluminum chelate compound, pulverized inorganic material consisting essentially of a mixture of powder containing at least one member selected from the group consisting of aluminum phosphate, zinc molybdate and calcium carbonate, plate-shaped powder principally containing aluminum silicate or magnesium silicate, and metallic zinc powder. The composition exhibits excellent rust-preventing performance in a temperature range spreading from a low temperature to a high temperature, as a heat-resisting painting material for use on an exhaust pipe connected with a motor car engine. Upon applying said heat-resisting coating composition onto a metal surface, it is effective for enhancing adhesion to preliminarily form fine protrusions having "turn-rounds" on the metal surface.
Description
This is a division of application Ser. No. 769,838 filed Aug. 27, 1985 and now U.S. Pat. No. 4,657,963.
1. Field of the Invention
The present invention relates to a heat-resistant coating composition and a heat-resistant coat making use of said composition, and more particularly to a heat-resistant coating composition and a coat consisting of said composition which has stable rust-proofness even after it has been exposed to any temperature within a temperature range of -50° C.-650° C. for a long period.
2. Description of the Prior Art
Recently, speed-up of the rotational speed of an engine and reduction of the weight and the size of an exhaust pipe in a motor-cycle, a motor tricycle, a motor car, etc. have advanced, and the surface temperature of an exhaust pipe has become high as compared to that in the prior art to such extent that it exceeds the limit temperature of 550° C. of the heat-resistant rust-preventing paint used in the prior art and reaches 650° C.
An exhaust pipe of a motor car engine is composed of an exhaust pipe section connected to an exhaust manifold or directly to cylinder heads and a muffler (silencer); the closer a portion of the exhaust pipe is located to the engine, the larger temperature change to which said portion is exposed, and at the rear end portion of the muffler which is remote from the engine, the temperature change is 100° C. or lower. The condition of use of the exhaust pipe section close to the engine is especially severe, in a cold district it is used in the temperature range of, for instance, from an atmospheric temperature -30° C. to about 650° C. upon high speed rotation of the engine, and moreover, upon starting of the engine the temperature rises at a rate of about 600° C. per minute and reaches the highest temperature after only about 70 seconds.
In addition, during running of a vehicle, pebbles, sand, mud, water, etc. splashed by wheels would collide with the surface of the exhaust pipe, hence an impact force or a thermal impact would act upon the surface, while during stoppage of the vehicle, the exhaust pipe is exposed to a corrosive environment caused by rain water, salty water or dew water produced at night, and so, corrosion of the exhaust pipe proceeds.
Heretofore, as a heat-resisting coating material for protecting an exhaust pipe, a silicone series heat-resisting paint has been used, and the composition of the paint consists principally of silicone resin or modified silicone resin, metallic zinc and inorganic pigment. A metal surface to which this composition is to be applied, is preliminarily roughened by subjecting it to a shot blast treatment, the above-mentioned composition is applied on the roughened surface to form a lower layer, then a composition consisting of silicone resin, metal oxides and inorganic pigment is superposed thereon, and thereby a heat-resisting coat is formed.
The principle of rust-prevention by means of this heat-resisting coat is such that in the low temperature range, invasion of water and salts which act as corrosive media to the surface of metal is prevented by the coat, and after heating, it is aimed to realize a sacrificial anodic effect of metallic zinc making use of a potential difference between the base metal and zinc. In the case of the heat-resisting coat in the prior art, there exists a temperature range where either of the above-mentioned rust-preventing effects appears poorly, and more particularly, a rust-prevention power after heated in the temperative range of 200° C.-300° C. is poor, and so, on the practically used exhaust pipe, often rust was produced at an early time.
As a result of seeking for the cause of the above-mentioned defects, the following has been clarified:
○1 Even under the condition that the lower layer coating material has been heated up to 380° C., metallic zinc particles contained therein are wrapped by carbide coating films of resin, hence assembled cracks (See FIG. 1) would appear while the rust-preventing effect relying upon the sacrificial anode does not appear, and so, a shielding effect for the corrosive media is lost.
○2 The thickness of the coat is 60μ or less, and so, in the case where the height of the protrusions formed on the metal surface by the roughening treatment exceeds 40μ, the thickness of the coating layer covering the protruded portions is remarkably reduced, hence the top portions of the protrusions are apt to be exposed, and thus rusting is promoted.
A principal object of the present invention is to provide a heat-resisting coating composition which does not produce assembled cracks even when it is heated, in which a sacrificial anodic effect relying upon metallic zinc can be fully achieved, and which has an excellent rust-preventing property.
Another object of the present invention is to provide a heat-resisting coat which is applied on a surface of metal subjected to a special surface roughening treatment, which is hard to be peeled off and which has an excellent rust-preventing property.
Characteristic features of the present invention will become more apparent from perusal of the following detailed description of the invention with reference to the accompanying drawings.
FIG. 1 is a photograph showing the state where cracks have been produced by heating a publicly known heat-resisting coat containing particles of inorganic material powder;
FIG. 2 is a photograph showing the state where particles of a pulverized inorganic material are exposed by heating a heat-resisting coat according to the present invention;
FIG. 3 is a cross-section view of a metal surface portion attained through a surface roughening treatment in the prior art;
FIG. 4 is a cross-section view showing the state where a heat-resisting coat has been applied onto the metal surface shown in FIG. 3;
FIG. 5 is a cross-section view showing the state where a heat-resisting coat has been applied onto a metal surface attained through a surface roughening treatment relevant to the present invention; and
FIGS. 6 to 9 are comparative diagrams showing the effects of heat-resisting coats according to the present invention.
The heat-resisting coating composition according to the present invention comprises pulverized inorganic material consisting essentially of a mixture of powder containing at least one compound selected from the group consisting of aluminium phosphate, zinc molybdate and calcium carbonate, plate shaped powder particles consisting mostly of aluminium silicate or magnesium silicate, and metallic zinc powder, which inorganic material is bound by modified silicone resin to which an aluminium chelate compound has been added. In this composition, a network of cracks is not generated even when the composition is heated. The strain caused by heating is dispersed among the particles of the powder, resulting in exposure of the surface of metallic zinc in the pulverized inorganic material, hence a sacrificial anodic effect can be revealed, and also invasion of water and salts which act as corrosive media can be surely prevented.
When a mixture of silicone resin or modified silicone resin and powder of an inorganic material (a mixture used in the prior art) is coated on a metal surface and is heated, the organic groups which are on the side of the Si-O-Si chain in the silicone resin and modified resin are oxidized and escape in the form of gas, leaving residual carbon, and so, at a high temperature the particles of the inorganic material are bound with carbon in the coating film formed by the Si-O-Si chain. In this coating film, there are numerous networks of cracks (See FIG. 1), and hence corrosive media would easily invade the metal surface.
According to the present invention, such problems in the prior art have been resolved by employing an aluminium chelate compound as a resin binder, and by employing plate-shaped powder particles as a component of the inorganic material. The plate-shaped powder particles result from cleavage along a plane in the crystal structure of a mineral.
A preferable compounding ratio of the heat-resistant coating composition according to the present invention is as follows:
○1 modified silicone resin+aluminium chelate compound--20-50 weight % ##EQU1##
○2 pulverized inorganic material--50-80 weight %
In order to improve the shielding effect (the effect of preventing invasion of corrosive media) of silicone resin, it is favorable that any one of phenol resin, epoxy resin, acrylic resin and polyester resin or a mixture of them (called modified resin) be present in the silicone resin to the extent 20-40 weight % (this being called modified silicone resin) and to add an aluminium chelate compound thereto. For this aluminium chelate compound, ethylacetate aluminium di-isoprolylate or aluminium tris-ethylacetoacetate is favourable. The aluminium chelate compound functions as a catalyst for inter-molecule bonding in the resin, and it has the effect that by reducing the presence of unbonded molecules thermal decomposition loss is decreased and strength is improved, resulting in reduction of the network of cracks over the surface of the pulverized inorganic material (See FIG. 2). Also, the addition of modified resin to silicone resin is for the purpose of reinforcing adhesion when the composition is heated up to 350° C.-450° C. and giving it basic strength to reduce particle surface cracks.
Furthermore, in order to reinforce rust-preventing power in the case where the heat-resisting coating composition is heated up to 200° C.-400° C., it is necessary that any one of aluminium phosphate, zinc molybdate and calcium carbonate or a mixture of them be present in the pulverized inorganic material to the extent of 20-55 weight %, and also it is desirable that the plate-shaped powder particles be present in the pulverized inorganic material to the extent of 2-30 weight %. As these plate-shaped powder particles, mica powder principally consisting of aluminium silicate or talc principally consisting of magnesium silicate are effective, and these powders form a layer overlapping with other powder particles in the bonded coating composition. This layer has an excellent shielding effect and a capability of preventing a network of cracks.
In addition, with regard to the metallic zinc powder to be used as a sacrificial anode, it is necessary that it be present to the extent of 40-70 weight % in the above-described pulverized inorganic material and preferrably 20-56 weight % in the coating composition.
On the other hand, the condition of the metal surface on which the above-mentioned heat-resisting coating composition is to be applied is also important. Heretofore, as a method for roughening a metal surface, a shot-blast process and a sand blast process have been employed, and on the surface of metal treated through these processes are formed protrusions 1 having a cross-section configuration as shown in FIG. 3. In the case of such a surface, since the difference in height between a protruded portion and the recessed portion is large, the thickness of a coat applied to the recessed portion is large, but that applied to the protruded portion is small, resulting in lowering of rust-preventing power, and even if the protrusions and recesses are formed finely, as the shape of the protrusions 1 is a simple spike type, adhesion of the coat is weak and it is apt to be peeled off when it is heated up to a high temperature (See FIG. 4. In this figure, referrence numeral 2 designates a coat.).
In order to obviate such shortcomings, according to the present invention, fine protrusions 3 having "turn-rounds" (overhanging portions) 4 are formed on the surface of metal so as to improve adhesion of the coat 5 (FIG. 5). Since the protrusion 3 is formed as bent into the recessed portion by collapsing a tip portion of a simple spike-shaped protrusion and thus has a small height and a "turn-round" 4, an excellent heat-resisting power and an excellent high-temperature adhesion can be provided. In contrast to the fact that in the case of the metal surface configuration as shown in FIG. 3, even if the base metal is stainless steel or nickel plating having little tendency for thermal oxidation, a coat would peel off when heated up to 550° C. or higher, a coat applied to base metal having a group of fine protrusions with "turn-rounds" 4 formed thereon would not peel off even if it is heated up to 650° C. for a long period of time.
For forming such protrusions 3 on the surface of metal, it is sufficient to form fine protrusions and recesses on the metal surface by blasting metal particles, alumina particles, sand particles or the like having sharp corners and a diameter of 0.3 mm or less (particles which are called "grit") onto the metal surface with a high pressure by means of a blasting machine (for example, that of rotary blade type or compressed air type), and then collapsing the tip ends of the already formed fine protrusions by blasting spherical particles or rectangular particles of glass, metal or the like having a diameter of 0.3 mm or less with an extremely low pressure (See Example VIII).
Now, examples of tests conducted to confirm the effects and advantages of the present invention will be set forth. It is to be noted that in the respective tables attached to this specification and in the foot notes of the tables, numerals (1)*, (2)*, . . . (9)* are added for the purpose of clarifying names of the materials used and their compounding proportions, and operation processes for the tests. The explanation for the respective numerals are given in Table-16.
With respect to Samples 1-1, 1-2, . . . , 1-5 for which compounding proportions of aluminium chelate compound, silicone resin, modified resin and pulverized inorganic materials are varied, the heat-resisting adhesivness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-1, and the test results are shown in Table 2. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of modified resin contained in modified silicone resin consisting of silicone resin and modified resin falls in the range of 20-40 weight %.
With respect to respective Samples 2-1, 2-2, . . . , 2-5, the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-3, and the test results are shown in Table-4. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of pulverized inorganic material contained in the coat is 50-80 weight %, or when the proportion of "modified silicone resin+aluminium chelate compound" contained in the coat is 20-50 weight %.
With respect to respective Samples 3-1, 3-2, . . . , 3-6, the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-5, and the test results are shown in Table-6. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of aluminium chelate compound relative to the mixture of aluminium chelate compound and modified silicone resin falls in the range of 0.5-4 weight %.
With respect to respective Samples 4-1, 4-2, . . . , 4-6, the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-7, and the test results are shown in Table-8. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of metallic zinc powder contained in the pulverized inorganic material (zinc molybdate+cleaving scale-shaped powder+metallic zinc powder) is 40-70 weight %.
With respect to respective Samples 5-1, 5-2, . . . , 5-6, the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-9, and the test results are shown in Table 10. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of plate-shaped powder particles (mica+talc) contained in the pulverized inorganic material (zinc molybdate+metallic zinc powder+plate-shaped powder) particles is 2-30 weight %.
With respect to respective Samples 6-1, 6-2, . . . , 6-5, the heat-resisting adhesiveness and the heat-resisting rust-proofness were investigated. The compounding proportions are shown in Table-11, and the test results are shown in Table-12. According to the respective tables, the heat-resisting adhesiveness and the heat-resisting rust-proofness of the heat-resisting coat are excellent when the proportion of zinc molybdate contained in the pulverized inorganic material (zinc molybdate+metallic zinc powder+plate-shaped powder) particles is 20-50 weight %.
Samples A, B, C and D have the resin component in the coat varied, Samples A and C employ modified silicone resin, and especially in Sample A the resin component is added with aluminium chelate compound. In addition, in Samples A-1, B-1, C-1, and D-1, in place of silica which is an inorganic material component in Samples A, B, C and D, respectively, "silica+zinc powder" is used. Furthermore, in Samples A-2, B-2, C-2 and D-2, the silica contents in Samples A-1, B-1, C-1 and D-1 are reduced, and condensed aluminium phosphate, zinc molybdate and calcium carbonate are added in place of them. In Samples A-3, B-3, C-3 and D-3, the silica contents in Samples A-2, B-2, C-2 and D-2 are reduced, and mica and talc are added in place of them.
The compounding proportions of these samples are shown in Table-13 and Table-14, and the test results for the heat-resisting corrosion-proofness of the respective Samples A . . . D, A-1 . . . D-1, A-2 . . . D-2, and A-3 . . . D-3 are shown, respectively, in FIGS. 6, 7, 8 and 9.
With reference to FIG. 6, it can be seen that the rust-preventing power of modified silicone resin to which an aluminium chelate compound is added is excellent. In addition, with reference to FIG. 7, it can be seen that the corrosion-proofness at a high temperature can be improved by adding zinc powder, and in the case of Samples A-1 and C-1 in which zinc powder is added to modified silicone resin, the rust-preventing effect relying upon zinc appears at a temperature that is lower by about 60° C. as compared to Sample B-1 in which zinc powder is added to silicone resin. Furthermore, with reference to FIG. 8, it is seen that the effects of condensed aluminium phosphate, zinc molybdate and calcium carbonate appear at 200° C.-400° C., and with reference to FIG. 9, it can be seen that plate-shaped powder particles (mica powder and talc) improve the rust-preventing power at 300° C.-400° C.
With respect to a heat-resisting coating film in the prior art and a coat according to the present invention, respectively, tests for the rust-preventing power and the adhesiveness were conducted while varying the conditions (roughness) of the base metal surface. Here it is to be noted that the above-referred "heat-resisting coating film in the prior art" means a coating film including, as a lower layer, a composition consisting of 30 wt.% silicone resin, 8 wt.% condensed aluminium phosphate, 8 wt.% zinc molybdate, 8 wt.% calcium carbonate, 35 wt.% zinc powder and 11 wt.% silica and another composition superposed thereon consisting of 26.3 wt.% silicone resin, 28.1 wt.% metal oxides, 19.3 wt.% silica and 26.3 wt.% talc, and that the above-referred "coat according to the present invention" means a coating film including, as a lower layer, a composition consisting of 20.4 wt.% silicone resin, 2.6 wt.% epoxy resin, 1.7 wt.% acrylic resin, 2.6 wt.% phenol resin, 1.7 wt.% polyester resin, 1 wt.% aluminium chelate compound, 8 wt.% condensed aluminium phosphate, 8 wt.% zinc molybdate, 8 wt.% calcium carbonate, 3 wt.% mica powder, 3 wt% talc, 35 wt.% zinc powder and 5 wt.% silica, and another composition superposed thereon consisting of 26.3 wt.% silicone resin, 28.1 wt.% metal oxides, 19.3 wt.% silica and 26.3 wt.% talc. According to Table-15 which shows the results of these tests, it can be seen that only the test No. 8-6 is satisfactory with respect to the rust-preventing power on the surface of iron and the adhesiveness (at 650° C.) to the nickel-plated surface. Accordingly, an exhaust pipe with a heat-resisting coat that is excellent in heat-resisting corrosion-proofness and is cheap, can be provided by employing nickel-plated base material in the exhaust pipe section close to the engine and employing iron in the muffer section.
As will be apparent from the above description, in the heat-resisting coat according to the present invention, a network of cracks would not be produced by heating, the surface of the metallic zinc particles in the pulverized inorganic material can be easily exposed, resulting in a sacrificial anodic effect, and invasion of corrosive media can be surely prevented. Moreover, the same heat-resisting coat applied onto a base metal surface provided with a group of fine protrusions having "turn-rounds" would hardly peel off even at a high temperature and thus reveals excellent corrosion proofness.
TABLE 1
__________________________________________________________________________
(Compounding Proportions)
Sample 1-1 1-2
1-3
1-4
1-5
__________________________________________________________________________
components
aluminium chelate (1)* 0.4
0.4
0.4
0.4
0.4
silicone resin 34 32 28 24 22
modified resin (2)* 6 8 12 16 18
pulverized inorganic material (4)*
60 60 60 60 60
##STR1## 15%
20 30 40 45
Total 100.4
100.4
100.4
100.4
100.4
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 2
______________________________________
(Test Results)
Sample
Test Item 1-1 1-2 1-3 1-4 1-5
______________________________________
Heat-resisting adhesiveness (8)*
x O O O x
Heat-resisting rust-proofness (9)*
x O O O x
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*
TABLE 3
__________________________________________________________________________
(Compounding Proportions)
Sample 2-1 2-2 2-3 2-4 2-5
__________________________________________________________________________
Components
pulverized inorganic material (4)*
90 80 70 50 40
modified silicone resin (3)*
9.9 19.8
29.7
49.5
59.4
aluminium chelate (1)*
0.1 0.2 0.3 0.5 0.6
Content of pulverized inorganic material
90% 80 70 50 40
Total 100.0
100.0
100.0
100.0
100.0
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 4
______________________________________
(Test Results)
Sample
Test Item 2-1 2-2 2-3 2-4 2-5
______________________________________
Heat-resisting adhesiveness (8)*
x O O O x
Heat-resisting rust-proofness (9)*
x O O O x
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*.
TABLE 5
__________________________________________________________________________
(Compounding Proportions)
Sample 3-1 3-2
3-3
3-4
3-5
3-6
__________________________________________________________________________
Components
aluminium chelate (1)*
0.2 0.5
1.0
3 4 4.5
modified silicone resin (3)*
99.8
99.5
99.0
97
96
95.5
pulverized inorganic material (4)*
233 233
233
233
233
233
##STR2## 0.2% 0.5 1.0
3 4 4.5
Total 333 333 333
333
333
333
__________________________________________________________________________
The above contents are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 6
______________________________________
(Test-Results)
Sample
Test Item 3-1 3-2 3-3 3-4 3-5 3-6
______________________________________
Heat-resisting adhesiveness (8)*
O O O O O x
Heat-resisting rust-proofness (9)*
x O O O O O
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*.
TABLE 7 __________________________________________________________________________ (Compounding Proportions) Sample 4-1 4-2 4-3 4-4 4-5 4-6 __________________________________________________________________________Components zinc molybdate 50 48 40 32 24 20 plate-shaped powder 15 12 10 8 6 5 metallic zinc powder 35 40 50 60 70 75 modified silicone resin (3)* 43 41 38 34 31 29 aluminium chelate (1)* 0.43 0.41 0.38 0.34 0.38 0.29 Content of metallic zinc powder* 35% 40 50 60 70 75 Total 143.43 141.41 138.38 134.34 131.38 129.29 __________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat. ##EQU2##
TABLE 8
______________________________________
(Test Results)
Sample
Test Item 4-1 4-2 4-3 4-4 4-5 4-6
______________________________________
Heat-resisting adhesiveness (8)*
O O O O O O
Heat-resisting rust-proofness (9)*
x O O O O x
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*
TABLE 9
__________________________________________________________________________
(Compounding Proportions)
Sample 5-1 5-2 5-3 5-4 5-5 5-6
__________________________________________________________________________
Components
zinc molybdate 33 33 30 27 23 22
metallic zinc powder
66 65 60 53 47 43
cleaving scale-shaped powder
1 2 10 20 30 35
modified silicone resin (3)*
31 32 35 39 42 45
aluminium chelate (1)*
0.3 0.3 0.4 0.4 0.4 0.5
Content of plate-shaped powder*
1% 2 10 20 30 35
Total 131.3
132.3
135.4
139.4
142.4
145.5
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat. ##EQU3##
TABLE 10
______________________________________
(Test Results)
Sample
Test Item 5-1 5-2 5-3 5-4 5-5 5-6
______________________________________
Heat-resisting adhesiveness (8)*
x O O O O O
Heat-resisting rust-proofness (9)*
x O O O O x
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*.
TABLE 11
__________________________________________________________________________
(Compounding Proportions)
Sample 6-1 6-2 6-3 6-4 6-5
__________________________________________________________________________
Components
zinc molybdate
15 20 30 50 55
metallic zinc powder
44 60 52 37 34
plate-shaped powder
21 20 18 13 11
modified silicone resin (3)*
32 37 39 42 42
aluminium chelate (1)*
0.3 0.4 0.4 0.4 0.4
Content of zinc molybdate
15% 20 30 50 55
Total 132.3
137.4
139.4
142.4
142.4
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 12
______________________________________
(Test-Results)
Sample
Test Item 6-1 6-2 6-3 6-4 6-5
______________________________________
Heat-resisting adhesiveness (8)*
O O O O O
Heat-resisting rust-proofness (9)*
x O O O x
______________________________________
The test was conducted with respect to the respective ones of the coats which had been heated through the process (7)*.
TABLE 13
__________________________________________________________________________
(Compounding Proportions)
Sample
Components A B C D A-1
B-1
C-1
D-1
__________________________________________________________________________
modified resin (2)*
-- -- -- 30 -- -- -- 30
silicone resin
-- 30 -- -- -- 30 -- --
modified silicone resin (3)*
29 -- 30 -- 29 -- 30 --
aluminium chelate (1)*
1 -- -- -- 1 -- -- --
zinc powder -- -- -- -- 35 35 35 35
silica 70 70 70 70 35 35 35 35
Total 100
100
100
100
100
100
100
100
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 14
__________________________________________________________________________
(Compounding Proportions)
Sample
Materials A-2
B-2
C-2
D-2
A-3 B-3 C-3 D-3
__________________________________________________________________________
modified resin (2)*
-- -- -- 30 -- -- -- 30
silicone resin -- 30 -- -- -- 30 -- --
modified silicone resin (3)*
29 -- 30 -- 29 -- 30 --
aluminium chelate (1)*
1 -- -- -- 1 -- -- --
condensed aluminium phosphate
8 8 8 8 8 8 8 8
zinc molybdate 8 8 8 8 8 8 8 8
calcium carbonate
8 8 8 8 8 8 8 8
mica powder -- -- -- -- 3 3 3 3
talc -- -- -- -- 3 3 3 3
zinc powder 35 35 35 35 35 35 35 35
silica 11 11 11 11 5 5 5 5
Total 100
100
100
100
100 100 100 100
__________________________________________________________________________
The above components are dispersed through the process (5)* and then applied through the process (6)* to form a coat.
TABLE 15
__________________________________________________________________________
Heat-resisting paint
Coat according to
in the prior art
the present invention
Roughness Control
Coat →
Rust-
Adhesiveness
Rust-
Adhesiveness
Particle Performance
→
proofness
Nickel-
proofness
Nickel-
Test Shape
Particle
Base Material
→
Iron plated Iron plated
Number
↓
Diameter
Temperature
→
350° C.
650° C.
350° C.
650° C.
__________________________________________________________________________
8-1 spherical
0.5 mm
Low pressure treat-
→
x x x x
ment not performed
8-2 rectan-
0.5 mm
Low pressure treat-
→
x x x x
gular ment not performed
8-3 rectan-
0.5 mm
Low pressure treat-
→
x x O x
gular ment performed
8-4 spherical
0.3 mm
Low pressure treat-
→
x x O x
ment not performed
8-5 rectan-
0.2 mm
Low pressure treat-
→
x x O x
gular ment not performed
8-6 rectan-
0.2 mm
Low pressure treat-
→
x x O O
gular ment performed
Test Results
__________________________________________________________________________
TABLE 16
__________________________________________________________________________
.sup.(1) *aluminum chelate
##STR3##
.sup.(2) *modified resin
epoxy resin (30%), acrylic resin (20%), phenol resin (30%),
polyester resin (10%) (The numerals represent compounding
proportions)
.sup.(3) *modified silicone
silicone resin (79%), modified resin (30%)
resin
.sup.(4) *pulverized inorganic
condensed aluminum phosphate (20%), zinc molybdate (15%),
material calcium carbonate (15%), zinc powder (40%), mica powder
(2%),
talc (2%), silica (5%)
.sup.(5) *process for dispersing
The coating composition is dispersed through the steps of
a coating composition
mixing the pulverized inorganic material into a resin
solution
in which the resin is resolved by an organic solvent,
kneading the
mixture by means of a ball mill, a triple roll, etc. until
an
average particle diameter becomes 1.5μ, and then
dispersing
the kneaded mixture into a solution.
.sup.(6) *process for coating
The organic solvent solution containing the coating
composition
is appropriately thinned by a thinner, and then it is coated
by spraying.
As the base material, a normal steel plate of 1 mm in
thickness is employed, then it is subjected to sand blast or
grit
blast of 0.2 mm grits to an excessive extent, and the
finished
surface is painted with the solution.
With regard to the thickness of the composition, it is
finished into a thickness in the range of 10˜20μ to
form a lower
layer, then a heat-resisting paint having the known
composition
consisting of 26.3 wt. % silicone resin, 28.1 wt. % metal
oxides,
19.3 wt. % silica and 26.3 wt. % talc, is applied in a
thickness
of 10˜30μ onto the lower layer to form an upper
layer and then
it is baked and dried at 180° C. for 30 minutes.
.sup.(7) *process for heating
The coats are heated respectively, with combinations of
temperature and time of 150° C. × 200 Hours,
200° C. × 200 Hours, - 250° C. ×
200 Hours, 300° C. × 200 Hours, 350° C.
× 200 Hours,
400° C. × 200 Hours, 450° C. × 200
Hours, 500° C. × 200 Hours,
550° C. × 200 Hours, 600° C. × 200
Hours and 650° C. × 200 Hours.
.sup.(8) *adhesiveness
On the surface of the painted film are formed 100 lattice
lines at an interval of 1 mm having a depth reaching the
base
material with a cutter, an adhesive tape is attached onto
the
surface and it is suddenly peeled off.
Determination: a number of lattice squares where more than
1/2 of a lattice square painted film is peeled off is
counted, and
if it is five or more the adhesiveness is determined to be
no
good, and the result is marked x. Whereas if it is fewer
than
5 the adhesiveness is determined to be normal, and the
result
is marked O.
.sup.(9) *rust-proofness
On the surface of the painted film are formed cross-cuts
reaching the base metal with a cutter, and spraying is
carried
out for 72 hours continuously by means of a JIS salt spray
tester.
Thereafter, the sample is taken out, moisture is dried at
the
room temperature, an adhesive tape is attached to the cut
portion
and then it is peeled off suddenly.
Determination: when the peeled rust generated by the test
is limited to within 2 mm on one side from the cut portion,
the
rust-proofness is determined to be normal, and the result is
marked O, but when it exceeds the limit, the rust-proofness
is
determined to be no good, and the result is marked x.
As known processes of roughness control practiced in the
prior art, a shot blast process and a sand blast process
have
been known. On the metal surface obtained by practicing
these
processes are formed protrusions and recesses as shown in
FIG.
3, but protrusions having "turn-rounds" as shown in FIG. 5
cannot be formed. Even if the latter protrusions should
exist,
the number of the protrusions is few and they are present
only
locally. Hence, the desired effect cannot be
__________________________________________________________________________
obtained.
Claims (3)
1. A heat-resistant coat applied onto a metal surface provided with fine protrusions having overhanging portions, said coat being composed of a lower layer and an upper layer,
wherein said lower layer is formed from a coating composition comprising:
(a) 50-80% by weight of a pulverized inorganic material consisting essentially of (i) a mixture of powder particles consisting essentially of at least one compound selected from the group consisting of aluminum phosphate, zinc molybdate and calcium carbonate, (ii) plate-shaped powder particles consisting essentially of aluminum silicate or magnesium silicate, and (iii) metallic zinc powder, wherein the amount of the mixture of powder particles (i) is 20-55% by weight of the pulverized inorganic material, and the amount of metallic zinc powder is 40-70% by weight of the pulverized inorganic material; and
(b) 20-50% by weight of a mixture of a modified silicone resin and an aluminum chelate compound selected from the group consisting of ethyl acetate aluminum di-isopropylate and aluminum tri-ethylacetoacetate, wherein the amount of aluminum chelate is 0.5-4% by weight of the mixture (b), and the modified silicone resin consists of 20-40% by weight of at least one resin selected from the group consisting of phenol resin, epoxy resin, acrylic resin and polyester resin and 80-60% by weight of a silicone resin;
said pulverized inorganic material (a) being bound by said mixture (b) of modified silicone resin and aluminum chelate compound; and
wherein said upper layer is formed from a heat resistant coating composition consisting essentially of silicone resin and metal oxides.
2. A heat-resistant coat as claimed in claim 1, characterized in that said fine protrusions having overhanging portions are formed through the steps of blasting particles having corners and a diameter of 0.3 mm or less onto the metal surface with a strong pressure, and thereafter blasting spherical or rectangular particles having a diameter of 0.3 mm or less with a low pressure.
3. A heat-resisting coat as claimed in claim 1, characterized in that said modified silicone resin is prepared by compounding 20-40 weight % of at least one resin selected from the group consisting of phenol resin, epoxy resin, acrylic resin and polyester resin with silicone resin so as to amount to 100 weight % in total.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59177544A JPS6198773A (en) | 1984-08-28 | 1984-08-28 | Heat-resistant coating composition and heat-resistant coated material |
| JP59-177544 | 1984-08-28 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/769,838 Division US4657963A (en) | 1984-08-28 | 1985-08-27 | Heat-resistant coating composition and heat-resistant coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4746568A true US4746568A (en) | 1988-05-24 |
Family
ID=16032802
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/769,838 Expired - Lifetime US4657963A (en) | 1984-08-28 | 1985-08-27 | Heat-resistant coating composition and heat-resistant coat |
| US07/013,815 Expired - Lifetime US4746568A (en) | 1984-08-28 | 1987-02-12 | Heat-resistant coating composition and heat-resistant coat |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/769,838 Expired - Lifetime US4657963A (en) | 1984-08-28 | 1985-08-27 | Heat-resistant coating composition and heat-resistant coat |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US4657963A (en) |
| EP (1) | EP0176251B1 (en) |
| JP (1) | JPS6198773A (en) |
| DE (1) | DE3577209D1 (en) |
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-
1984
- 1984-08-28 JP JP59177544A patent/JPS6198773A/en active Granted
-
1985
- 1985-08-27 EP EP85306045A patent/EP0176251B1/en not_active Expired - Lifetime
- 1985-08-27 US US06/769,838 patent/US4657963A/en not_active Expired - Lifetime
- 1985-08-27 DE DE8585306045T patent/DE3577209D1/en not_active Expired - Lifetime
-
1987
- 1987-02-12 US US07/013,815 patent/US4746568A/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JPS6335183B2 (en) | 1988-07-13 |
| EP0176251A2 (en) | 1986-04-02 |
| DE3577209D1 (en) | 1990-05-23 |
| EP0176251A3 (en) | 1987-09-16 |
| US4657963A (en) | 1987-04-14 |
| EP0176251B1 (en) | 1990-04-18 |
| JPS6198773A (en) | 1986-05-17 |
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